EP0606859B1 - Process to maintain or to improve the mechanical properties of aromatic copolyamide fibers in alkaline medium and articles containing these fibers - Google Patents

Process to maintain or to improve the mechanical properties of aromatic copolyamide fibers in alkaline medium and articles containing these fibers Download PDF

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Publication number
EP0606859B1
EP0606859B1 EP19940100194 EP94100194A EP0606859B1 EP 0606859 B1 EP0606859 B1 EP 0606859B1 EP 19940100194 EP19940100194 EP 19940100194 EP 94100194 A EP94100194 A EP 94100194A EP 0606859 B1 EP0606859 B1 EP 0606859B1
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mol
structural units
formula
multifilaments
recurring
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EP19940100194
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German (de)
French (fr)
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EP0606859A1 (en
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Richard Dr. Neuert
Georg-Emerich Dr. Miess
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Hoechst AG
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the present invention relates to a method for obtaining or Improving the mechanical properties of aromatic fibers Copolyamides in alkaline media, i. H. maintaining or increasing the Fiber tensile strength, and those moldings containing such fibers and hydraulically setting inorganic materials.
  • Aromatic polyamides (hereinafter called aramids) are called fiber-forming Known polymers with good chemical resistance.
  • Aramid fibers which are predominantly made up of para-monomers also stand out due to good mechanical properties such as high tensile strength and Elastic moduli.
  • the acid and alkali resistance of commercially available fibers from para-aramids leaves something to be desired, so that such fibers are not easily used for the production of composite materials that are strongly acidic or contain alkaline matrix materials.
  • the drop in tensile strength from Fibers made from such aramids when stored in strongly acidic or alkaline Media, such as sulfuric acid or caustic soda, is used with a partial Hydrolysis of the polymer's amide bonds explained (see H.H. Yang, Aromatic High-Strength Fibers, pp. 248-251 and S. 274-276, J. Wiley & Sons).
  • aromatic copolyamide which consists predominantly of para monomers is built up and in organic aprotic and polar Solvents is soluble "is a copolyamide in the context of this invention understand that in conventional solvents for polyamides, for example in N-methylpyrrolidone, at 25 ° C to at least 4 to 12 wt .-% particularly good is 5.0 to 7.5% by weight soluble, in addition to at least one aromatic Dicarboxylic acid component at least two aromatic diamine components having.
  • the dicarboxylic acid component is mainly, in particular more than 90 mol%, based on the total amount of dicarboxylic acid components in the polymer, from divalent aromatic radicals in which the carboxyl groups in para- or comparable coaxial or parallel Position.
  • At least one of the diamine components is derived from divalent ones aromatic residues whose amino groups are in para- or in comparable coaxial or parallel position; this Diamine component, which is also a mixture of different diamines Type can usually be at least 50 mol%, based on the total amount of the diamine components in the polymer, preferably more than 60 mol%, based on the total amount Diamine components in the polymer, contained in this.
  • At least one of the diamine components is derived from divalent ones aromatic residues whose amino groups are in an angled position to each other, for example in meta or in a comparable angled Position to each other; this diamine component, which is also a mixture various diamines of this type can usually be up to 50 mol%, based on the total amount of the diamine components in the polymer, preferably less than 40 mol%, based on the total amount Diamine components in the polymer, contained in this.
  • the necessary period of storage is in each case too determine, using routine procedures.
  • the aramid fibers treated or to be treated according to the invention become preferably in a mixture with cement, mortar, concrete, gypsum optionally in Combination with organic sealants - i.e. in building materials in broadest sense - used.
  • the storage medium is an aqueous slurry or Mixing of a hydraulically setting inorganic material, especially cement or concrete.
  • An aqueous mixture is very particularly preferred as the storage medium a hydraulically setting inorganic material and the Storage takes place after the fibers have been mixed in and shaped obtained molded mixture.
  • the stored aramid multifilaments are in the strongly alkaline Environment exposed to temperatures from 20 to 100 ° C, especially Temperatures from 20 to 60 ° C.
  • the service temperatures of the obtained Shaped bodies can be, for example, between -50 ° C and + 60 ° C.
  • the period of storage depends on the individual selected Conditions such as pH of the storage medium and storage temperature.
  • the final state is usually the increase in multifilaments within reached a few days. At higher temperatures it can take hours suffice.
  • the modulus of elasticity usually remains more or less constant.
  • These multifilaments are shaped articles with high compressive strengths and a high employment ratio can be established.
  • Aramid multifilaments are preferably used in the process according to the invention a, which is a prior to storage in the inorganic matrix
  • Types of these aramids are particularly preferably used, in which -Ar- and -Ar'- Are 1,4-phenylene.
  • the aramid multifilaments can be used to carry out the method according to the invention in the form of short cuts, staple fibers or continuous filaments be stored.
  • staple fibers have a staple length of 1.5 to 48 mm, preferably 3 to 24 mm, in particular 4 to 12 mm.
  • Shaped articles containing continuous filaments can, for example, be unidirectional reinforced molded body or reinforced molded body in the winding process.
  • Typical single fiber titers are above 1.0 dtex, preferably in the range from 1.7 to 15 dtex.
  • Continuous filaments are generally stored as multifilaments. Their Total titer is typically in the range from 840 to 18400 dtex. It was found that the increase in strength when using multifilaments with higher overall titles is more pronounced, which is why the use of such Multifilaments is particularly preferred.
  • the matrix is preferably in the form of an inorganic material, such as in the form from fine particles, such as gypsum, cement, limestone powder, to coarse particles, like sand, gravel and stones. Mixing into the inorganic material can done in a dry or moist state.
  • the introduction of multifilaments into the matrix can also be done in itself Known methods take place, for example by storing preformed Multifilament body with hydraulically setting materials; this result in the desired shaped body after setting. This is what it is about preferably unidirectionally reinforced molded articles or in Shaped body reinforced molding.
  • the multifilaments can be used in particular in the manufacture and Exploit the use of moldings, which consist of a combination of aramid multifilaments to be used according to the invention and an aqueous one Mixture of a hydraulically setting inorganic material produced will.
  • the invention therefore also relates to the moldings obtainable in this way.
  • multifilaments consist of a Aramid based on 100 mol% terephthalic acid, 25 mol% para-phenylenediamine, 25 mol% 1,4-bis (4-aminophenoxy) benzene and 50 mol% 3,3'-dimethylbenzidine (aramid I) or from an aramid based on 100 mol% terephthalic acid, 50 mol% para-phenylenediamine, 15 mol% 1,4-bis (4-aminophenoxy) benzene and 35 mole% 3,4'-diaminodiphenyl ether (aramid II) exist.
  • the fiber tow is spun by a conventional wet spinning method a polymer solution in N-methylpyrrolidone in a precipitation bath and a Post-treatment comprising washing, stretching and drying.
  • Example 9 shows the values for the untreated fiber.
  • Example No. 9 10th 11 12th PH value - 10th 12th 14
  • Example 17 shows the values for the untreated fiber.
  • multifilaments which consist of an aramid based on 100 mol% terephthalic acid, 50 mol% para-phenylenediamine and 50 mol% of 3,4'-diaminodiphenyl ether.
  • the multifilament is a customary process wet-spun and post-treated fiber cable.
  • the storage took place in Cement filtrate: Portland cement PZ 35 (200 g in 1 l water)
  • a fiber tow of filaments of the above-identified aramid with a total titer of 1700 dtex was stored for 24 hours in cement filtrate with a pH of 12.5 and at different temperatures.
  • the following table shows tensile strengths, moduli and elongations at break of the samples after storage.
  • Example 58 shows the values for the untreated fiber.
  • Example No. 58 59 60 61 Storage temperature (° C) - 22 60 95
  • a fiber cable made of filaments of the above-identified aramid with a total titre of 1700 dtex was stored for 24 hours in sodium hydroxide solution at different pH values at 60 ° C.
  • the following table shows tensile strengths, moduli and elongations at break of the samples after storage.
  • Example 62 shows the values for the untreated fiber.
  • Example No. 62 63 64 65 PH value - 10th 12th 14

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

The invention relates to a process for maintaining or increasing the tensile strength of fibres of aromatic copolyamides which are built up predominantly from para-monomers and are soluble in organic aprotic and polar solvents during storage in alkaline media. The process comprises the measures: a) production of fibres from said aromatic copolyamides by dry or wet spinning processes which are customary per se, b) aftertreatment of the resulting fibres in a manner which is known per se, and c) storage of the fibres in an aqueous environment which has a pH of at least 10 for at least a period of time and at a temperature such that the tensile strength of said fibres, based on the tensile strength of the fibres employed in step c), is at least retained or increased.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Erhalt oder zur Verbesserung der mechanischen Eigenschaften von Fasern aus aromatischen Copolyamiden in alkalischen Medien, d. h. den Erhalt oder die Erhöhung der Faserzugfestigkeit, und diejenigen Formkörper enthaltend solche Fasern und hydraulisch abbindende anorganische Materialien.The present invention relates to a method for obtaining or Improving the mechanical properties of aromatic fibers Copolyamides in alkaline media, i. H. maintaining or increasing the Fiber tensile strength, and those moldings containing such fibers and hydraulically setting inorganic materials.

Aromatische Polyamide (im folgenden Aramide genannt) sind als faserbildende Polymere mit guter Chemikalienbeständigkeit bekannt. Fasern aus Aramiden, welche überwiegend aus para-Monomeren aufgebaut sind, zeichnen sich ferner durch gute mechanische Eigenschaften, wie hohe Zugfestigkeiten und Elastizitätsmoduli aus.Aromatic polyamides (hereinafter called aramids) are called fiber-forming Known polymers with good chemical resistance. Aramid fibers, which are predominantly made up of para-monomers also stand out due to good mechanical properties such as high tensile strength and Elastic moduli.

Die Säure- und Alkalibeständigkeit handelsüblicher Fasern aus para-Aramiden läßt zum Teil zu wünschen übrig, so daß sich solche Fasern nicht ohne weiteres zur Herstellung von Verbundwerkstoffen einsetzen lassen, welche stark saure oder alkalische Matrixmaterialien enthalten. Der Abfall der Zugfestigkeit von Fasern aus solchen Aramiden bei der Lagerung in stark sauren oder alkalischen Medien, wie Schwefelsäure oder Natronlauge wird mit einer teilweisen Hydrolyse der Amidbindungen des Polymeren erklärt (vergl. H.H. Yang, Aromatic High-Strength Fibers, S. 248-251 undS. 274-276, J. Wiley & Sons). Es sind allerdings bereits Aramidfasern bekannt geworden, die eine gegenüber klassischen Aramidfasern verbesserte Säure- und Alkalibeständigkeit sowie eine geringe Feuchtigkeitsaufnahme aufweisen und deren Einsatz für die Verstärkung von Faserzement bereits vorgeschlagen worden ist (vergl. Technische Textilien, 35. Jahrgang, Oktober 1992, T128-T132).The acid and alkali resistance of commercially available fibers from para-aramids leaves something to be desired, so that such fibers are not easily used for the production of composite materials that are strongly acidic or contain alkaline matrix materials. The drop in tensile strength from Fibers made from such aramids when stored in strongly acidic or alkaline Media, such as sulfuric acid or caustic soda, is used with a partial Hydrolysis of the polymer's amide bonds explained (see H.H. Yang, Aromatic High-Strength Fibers, pp. 248-251 and S. 274-276, J. Wiley & Sons). However, aramid fibers have already become known, one against the other classic aramid fibers improved acid and alkali resistance as well as a have low moisture absorption and their use for reinforcement of fiber cement has already been proposed (see technical textiles, 35th year, October 1992, T128-T132).

Aus JP-A-58-151,363 ist bekannt, daß eine Sattdampfbehandlung von faserverstärkten Betonteilen zu einer erhöhten Zug- und Biegefestigkeit derselben führt. Grundvoraussetzung für eine derartige Behandlung ist, daß die Bauteile aus faserverstärktem Beton in einen Autoklaven passen, so daß nur relativ kleine Betonteile einer derartigen Behandlung unterzogen werden können.From JP-A-58-151,363 it is known that saturated steam treatment of fiber-reinforced concrete parts for increased tensile and bending strength the same leads. The basic prerequisite for such treatment is that the Components made of fiber-reinforced concrete fit into an autoclave, so that only relatively small concrete parts can be subjected to such a treatment.

Es wurde jetzt gefunden, daß Fasern aus bestimmten aromatischen Copolyamiden, welche hauptsächlich aus para-Monomeren aufgebaut sind und in organischen aprotischen und polaren Lösungsmitteln löslich sind, durch Behandlung mit stark alkalischen Umgebungen einen Erhalt oder eine Erhöhung ihrer Zugfestigkeit sowie anderer mechanischer Eigenschaften, wie Modul oder Reißdehnung, erfahren.It has now been found that fibers from certain aromatic Copolyamides, which are mainly composed of para monomers and are soluble in organic aprotic and polar solvents Treatment with strongly alkaline environments will maintain or increase their tensile strength and other mechanical properties such as module or Elongation at break, experienced.

Dieses Verhalten ist um so überraschender, als man aufgrund der Erfahrungen an vorbekannten para-Aramiden, welche lediglich in agressiven Medien, wie in konzentrierter Schwefelsäure löslich sind, nicht mit einem Anstieg bzw. Erhalt der mechanischen Eigenschaften sondern im Gegenteil mit einem Abfall dieser Eigenschaften in einer stark alkalischer Umgebung mit der Zeit zu rechnen hatte.This behavior is all the more surprising than one can from experience on previously known para-aramids, which are only found in aggressive media, such as in concentrated sulfuric acid are soluble, not with an increase or maintenance the mechanical properties but on the contrary with a decrease of these Properties over time in a strongly alkaline environment would have.

Die vorliegende Erfindung betrifft ein Verfahren zum Erhalt oder zur Erhöhung der Zugfestigkeit bei der Einlagerung von Multifilamenten aus aromatischen Copolyamiden, welche überwiegend aus para-Monomeren aufgebaut sind und in organischen aprotischen und polaren Lösungsmitteln löslich sind, in alkalische Medien, umfassend die Maßnahmen:

  • a) Herstellen von Multifilamenten aus besagten aromatischen Copolyamiden nach an sich üblichen Trocken- oder Naßspinnverfahren,
  • b) Nachbehandlung der erhaltenen Multifilamente in an sich bekannter Weise, und
  • c) Einlagerung von Multifilamenten mit einem Gesamttiter von 840 bis 18400 dtex in einer wässrigen Aufschlämmung oder Abmischung eines hydraulisch abbindenden anorganischen Materials, inbesondere Beton oder Zement, welche einen pH-Wert von mindestens 10, vorzugsweise von größer gleich 12, insbesondere von 12 bis 14, aufweist, zumindest für eine solche Zeitspanne und bei einer Temperatur von 20 bis 100°C, so daß die Zugfestigkeit besagter Fasern, bezogen auf die Zugfestigkeit der in Schritt c) eingesetzten Fasern, zumindest erhalten bleibt oder sich erhöht, wobei eine nachfolgende Sattdampfbehandlung in einem Autoklaven ausgeschlossen ist.
    • The present invention relates to a method for maintaining or increasing the tensile strength in the incorporation of multifilaments from aromatic copolyamides, which are predominantly composed of para-monomers and are soluble in organic aprotic and polar solvents, in alkaline media, comprising the measures:
  • a) producing multifilaments from said aromatic copolyamides by dry or wet spinning processes which are customary per se,
  • b) aftertreatment of the multifilaments obtained in a manner known per se, and
  • c) storage of multifilaments with a total titer of 840 to 18400 dtex in an aqueous slurry or mixture of a hydraulically setting inorganic material, in particular concrete or cement, which has a pH of at least 10, preferably greater than or equal to 12, in particular from 12 to 14 , has, at least for such a period of time and at a temperature of 20 to 100 ° C, so that the tensile strength of said fibers, based on the tensile strength of the fibers used in step c), is at least maintained or increased, with a subsequent saturated steam treatment in an autoclave is excluded.

    • Unter dem Begriff "aromatisches Copolyamid, welches überwiegend aus para-Monomeren aufgebaut ist und in organischen aprotischen und polaren Lösungsmitteln löslich ist" ist im Rahmen dieser Erfindung ein Copolyamid zu verstehen, das in herkömmlichen Lösungsmitteln für Polyamide, beispielsweise in N-Methylpyrrolidon, bei 25°C zu mindestens 4 bis 12 Gew.-% besonders gut zu 5,0 bis 7,5 Gew.-% löslich ist und das neben mindestens einer aromatischen Dicarbonsäurekomponente mindestens zwei aromatische Diaminkomponenten aufweist.Under the term "aromatic copolyamide, which consists predominantly of para monomers is built up and in organic aprotic and polar Solvents is soluble "is a copolyamide in the context of this invention understand that in conventional solvents for polyamides, for example in N-methylpyrrolidone, at 25 ° C to at least 4 to 12 wt .-% particularly good is 5.0 to 7.5% by weight soluble, in addition to at least one aromatic Dicarboxylic acid component at least two aromatic diamine components having.

    Dabei leitet sich die Dicarbonsäurekomponente hauptsächlich, insbesondere zu mehr als 90 Mol %, bezogen auf die Gesamtmenge an Dicarbonsäurekomponenten im Polymer, von zweiwertigen aromatischen Resten ab, bei denen die Carboxylgruppen in para- oder vergleichbarer koaxialer oder paralleler Stellung stehen.The dicarboxylic acid component is mainly, in particular more than 90 mol%, based on the total amount of dicarboxylic acid components in the polymer, from divalent aromatic radicals in which the carboxyl groups in para- or comparable coaxial or parallel Position.

    Ferner leitet sich mindestens eine der Diaminkomponenten von zweiwertigen aromatischen Resten ab, deren Aminogruppen sich in para- oder in vergleichbarer koaxialer oder paralleler Stellung befinden; diese Diaminkomponente, welche auch eine Mischung verschiedender Diamine dieses Typs darstellen kann, ist üblicherweise zu mindest 50 Mol %, bezogen auf die Gesamtmenge der Diaminkomponenten im Polymer, vorzugsweise zu mehr als 60 Mol %, bezogen auf die Gesamtmenge an Diaminkomponenten im Polymer, in diesem enthalten.Furthermore, at least one of the diamine components is derived from divalent ones aromatic residues whose amino groups are in para- or in comparable coaxial or parallel position; this Diamine component, which is also a mixture of different diamines Type can usually be at least 50 mol%, based on the total amount of the diamine components in the polymer, preferably more than 60 mol%, based on the total amount Diamine components in the polymer, contained in this.

    Mindestens eine der Diaminkomponenten leitet sich von zweiwertigen aromatischen Resten ab, deren Aminogruppen sich in gewinkelter Stellung zueinander befinden, beispielsweise in meta- oder in vergleichbarer gewinkelter Stellung zueinander; diese Diaminkomponente, welche auch eine Mischung verschiedender Diamine dieses Typs darstellen kann, ist üblicherweise zu bis zu 50 Mol %, bezogen auf die Gesamtmenge der Diaminkomponenten im Polymer, vorzugsweise zu weniger als 40 Mol %, bezogen auf die Gesamtmenge an Diaminkomponenten im Polymer, in diesem enthalten.At least one of the diamine components is derived from divalent ones aromatic residues whose amino groups are in an angled position to each other, for example in meta or in a comparable angled Position to each other; this diamine component, which is also a mixture various diamines of this type can usually be up to 50 mol%, based on the total amount of the diamine components in the polymer, preferably less than 40 mol%, based on the total amount Diamine components in the polymer, contained in this.

    Unter dem Begriff "übliches Trocken- oder Naßspinnverfahren" ist im Rahmen dieser Erfindung ein Herstellungsverfahren von Spinnfasern zu verstehen, bei dem im weitesten Sinne beim Verspinnen Lösungen des Polymeren in einem organischen aprotischen und polaren Lösungsmittel zur Verwendung kommen. Beispiele dafür sind Trockenspinnverfahren, Naßspinnverfahren oder Trockendüsen-Naßspinnverfahren.Under the term "usual dry or wet spinning" is in the frame this invention to understand a method of manufacturing staple fibers in which in the broadest sense when spinning solutions of the polymer in one organic aprotic and polar solvents are used. Examples of this are dry spinning processes, wet spinning processes or Dry nozzle wet spinning process.

    Unter dem Begriff "Nachbehandlung" sind im Rahmen dieser Erfindung an sich übliche Nachbehandlungen der ersponnenen Multifilamente zu verstehen, wie Verstrecken, Fixieren, Waschen, Präparieren und Trocknen.In the context of this invention, the term “aftertreatment” per se usual post-treatments of the spun multifilaments to understand how Stretching, fixing, washing, preparing and drying.

    Die notwendige Zeitspanne der Einlagerung ist jeweils im Einzelfall zu bestimmen, wobei Routineverfahren Anwendung finden können.The necessary period of storage is in each case too determine, using routine procedures.

    Die erfindungsgemäß behandelten oder zu behandelnden Aramidfasern werden bevorzugt in Mischung mit Zement, Mörtel, Beton, Gips gegebenenfalls in Kombination mit organischen Versiegelungsmitteln - also in Baustoffmitteln im weitesten Sinne - eingesetzt. The aramid fibers treated or to be treated according to the invention become preferably in a mixture with cement, mortar, concrete, gypsum optionally in Combination with organic sealants - i.e. in building materials in broadest sense - used.

    Bei dem Einlagermedium handelt es sich um eine wässrige Aufschlämmung oder Abmischung eines hydraulisch abbindenden anorganischen Materials, inbesondere Zement oder Beton.The storage medium is an aqueous slurry or Mixing of a hydraulically setting inorganic material, especially cement or concrete.

    Ganz besonders bevorzugt wird als Einlagermedium eine wässrige Abmischung eines hydraulisch abbindenden anorganischen Materials verwendet und die Lagerung erfolgt nach dem Einmischen der Fasern und der Formgebung der erhaltenen geformten Mischung.An aqueous mixture is very particularly preferred as the storage medium a hydraulically setting inorganic material and the Storage takes place after the fibers have been mixed in and shaped obtained molded mixture.

    Die eingelagerten Aramid-Multifilamente werden in der stark alkalischen Umgebung Temperaturen von 20 bis 100°C ausgesetzt, insbesondere Temperaturen von 20 bis 60°C. Die Gebrauchstemperaturen der erhaltenen Formkörper können beispielsweise zwischen -50°C und +60°C liegen.The stored aramid multifilaments are in the strongly alkaline Environment exposed to temperatures from 20 to 100 ° C, especially Temperatures from 20 to 60 ° C. The service temperatures of the obtained Shaped bodies can be, for example, between -50 ° C and + 60 ° C.

    Die Zeitspanne der Einlagerung hängt von den im Einzelfall gewählten Bedingungen ab, wie pH-Wert des Lagermediums und Lagertemperatur. Üblicherweise ist der Endzustand der Anstieg der Multifilamente innerhalb einiger Tage erreicht. Bei höheren Temperaturen können bereits Stunden ausreichen.The period of storage depends on the individual selected Conditions such as pH of the storage medium and storage temperature. The final state is usually the increase in multifilaments within reached a few days. At higher temperatures it can take hours suffice.

    Bei der Einlagerung tritt keine Verringerung der Zugfestigkeit der Multifilamente, sondern ein Erhalt oder insbesondere eine Erhöhung der Zugfestigkeit der Multifilamente ein; typische Werte der Erhöhung liegen im Bereich von 1 bis 20 %, vorzugsweise 2 bis 10 %.There is no reduction in the tensile strength of the multifilaments during storage, but a maintenance or in particular an increase in the tensile strength of the Multifilaments a; typical values of the increase are in the range from 1 to 20 %, preferably 2 to 10%.

    Neben der Zugfestigkeit erhöht sich in der Regel auch die Reißdehnung der Multifilamente. Der Elastizitätsmodul bleibt in der Regel mehr oder weniger konstant.In addition to the tensile strength, the elongation at break of the Multifilaments. The modulus of elasticity usually remains more or less constant.

    Aus diesen Multifilamente sind Formkörper mit hohen Druckfestigkeiten und einen hohen Arbeitsaufnahmeverhältnis herstellbar. These multifilaments are shaped articles with high compressive strengths and a high employment ratio can be established.

    Vorzugsweise setzt man im erfindungsgemäßen Verfahren Aramid-Multifilamente ein, die vor der Einlagerung in die anorganische Matrix eine Zugfestigkeit von mindestens 120 cN/tex, besonders 150 bis 290 cN/tex, insbesondere 150 bis 250 cN/tex, und einen Elastizitätsmodul, bezogen auf 100 % Dehnung, von mehr als 30 N/tex, besonders von 45 bis 100 N/tex, insbesondere von 45 bis 90 N/tex, aufweisen.Aramid multifilaments are preferably used in the process according to the invention a, which is a prior to storage in the inorganic matrix Tensile strength of at least 120 cN / tex, especially 150 to 290 cN / tex, in particular 150 to 250 cN / tex, and an elastic modulus, based on 100 % Elongation, from more than 30 N / tex, especially from 45 to 100 N / tex, in particular from 45 to 90 N / tex.

    Besonders bevorzugt setzt man im erfindungsgemäßen Verfahren aromatische Copolyamide ein, welche eine inhärente Viskosität von mindestens 2,4 dl/g, vozugsweise von 3,0 bis 6,5 dl/g (gemessen an Lösungen von 0,5 g Polyamid in 100 ml 98 gew%iger Schwefelsäure bei 25°C) und wenigstens die wiederkehrenden Struktureinheiten der Formeln I, II und III aufweisen (-OC-Ar-CO-NH-Ar'-NH-)

    Figure 00060001
    Figure 00060002
    worin -Ar- und -Ar'- zweiwertige organische Reste sind, bei denen die Valenzbindungen in para- oder vergleichbarer koaxialer oder paralleler Stellung zueinander stehen,

  • R einen C1-C4-Alkylrest, insbesondere Methyl, einen C1-C4-Alkoxyrest, insbesondere Methoxy oder ein Chloratom darstellt,
  • R'einen unsubstituierten oder alkylsubstituierten Methylenrest oder eine Gruppierung
  • -O-Ar-O- darstellt, worin -Ar- die oben definierte Bedeutung annimmt, und die Anteile der wiederkehrenden Struktureinheiten I, II und III, bezogen auf die Gesamtmenge dieser Struktureinheiten im Polymeren, innerhalb eines Bereiches liegen, der durch die folgenden Eckpunkte definiert ist:
  • Punkt Q entsprechend 5 Mol % Struktureinheiten der Formel I,
    45 Mol % Struktureinheiten der Formel II und 50 Mol % Struktureinheiten der Formel III,
  • Punkt R entsprechend 45 Mol % Struktureinheiten der Formel I,
    5 Mol % Struktureinheiten der Formel II und 50 Mol % Struktureinheiten der Formel III,
  • Punkt S entsprechend 60 Mol % Struktureinheiten der Formel I,
    35 Mol % Struktureinheiten der Formel II und 5 Mol % Struktureinheiten der Formel III,
  • Punkt T entsprechend 20 Mol % Struktureinheiten der Formel I,
    75 Mol % Struktureinheiten der Formel II und 5 Mol % Struktureinheiten der Formel III, und
  • Punkt U entsprechend 5 Mol % Struktureinheiten der Formel I,
    80 Mol % Struktureinheiten der Formel II und 15 Mol % Struktureinheiten der Formel III.
    • In the process according to the invention, particular preference is given to using aromatic copolyamides which have an inherent viscosity of at least 2.4 dl / g, preferably 3.0 to 6.5 dl / g (measured on solutions of 0.5 g of polyamide in 100 ml of 98 % sulfuric acid at 25 ° C) and at least the recurring structural units of the formulas I, II and III (-OC-Ar-CO-NH-Ar'-NH-)
    Figure 00060001
    Figure 00060002
    where -Ar- and -Ar'- are divalent organic radicals in which the valence bonds are in a para- or comparable coaxial or parallel position to one another,
  • R represents a C 1 -C 4 alkyl radical, in particular methyl, a C 1 -C 4 alkoxy radical, in particular methoxy or a chlorine atom,
  • R'is an unsubstituted or alkyl-substituted methylene radical or a group
  • -O-Ar-O-, in which -Ar- takes on the meaning defined above, and the proportions of the repeating structural units I, II and III, based on the total amount of these structural units in the polymer, are within a range defined by the following key points is defined:
  • Point Q corresponds to 5 mol% of structural units of the formula I,
    45 mol% of structural units of the formula II and 50 mol% of structural units of the formula III,
  • Point R corresponds to 45 mol% of structural units of the formula I,
    5 mol% of structural units of the formula II and 50 mol% of structural units of the formula III,
  • Point S corresponding to 60 mol% of structural units of the formula I,
    35 mol% of structural units of the formula II and 5 mol% of structural units of the formula III,
  • Point T corresponds to 20 mol% of structural units of the formula I,
    75 mol% of structural units of the formula II and 5 mol% of structural units of the formula III, and
  • Point U corresponds to 5 mol% of structural units of the formula I,
    80 mol% of structural units of the formula II and 15 mol% of structural units of the formula III.

    • Aramide dieses Typs sind aus der EP-A-199,090 bekannt, welche ebenfalls Gegenstand der vorliegenden Beschreibung ist.Aramids of this type are known from EP-A-199,090, which also The subject of the present description is.

    Besonders bevorzugt setzt man Typen dieser Aramide ein, worin -Ar- und -Ar'- 1,4-Phenylen sind, R Methoxy oder Chlor oder insbesondere Methyl darstellen und R' -O-1,4-Phenylen-O- ist, wobei die Mengenanteile der wiederkehrenden Struktureinheiten, bezogen auf die Gesamtmenge dieser Struktureinheiten innerhalb des Polymeren, innerhalb der folgenden Bereiche liegen:

  • wiederkehrende Struktureinheit der Formel I: 5 bis 60 Mol %,
  • vorzugsweise 15 bis 45 Mol %,
  • wiederkehrende Struktureinheit der Formel II: 5 bis 80 Mol %,
  • vorzugsweise 20 bis 70 Mol %, und
  • wiederkehrende Struktureinheit der Formel III: 5 bis 50 Mol %,
  • vorzugsweise 15 bis 50 Mol %.
    • Types of these aramids are particularly preferably used, in which -Ar- and -Ar'- are 1,4-phenylene, R is methoxy or chlorine or in particular methyl and R 'is -O-1,4-phenylene-O-, where the proportions of the recurring structural units, based on the total amount of these structural units within the polymer, are within the following ranges:
  • recurring structural unit of the formula I: 5 to 60 mol%,
  • preferably 15 to 45 mol%,
  • recurring structural unit of the formula II: 5 to 80 mol%,
  • preferably 20 to 70 mol%, and
  • recurring structural unit of the formula III: 5 to 50 mol%,
  • preferably 15 to 50 mol%.

    • Ebenfalls besonders bevorzugt setzt man im erfindungsgemäßen Verfahren aromatische Copolyamide ein, welche eine inhärente Viskosität von mindestens 2,4 dl/g, vorzugsweise 3,0 bis 6,5 dl/g (gemessen an Lösungen von 0,5 g Polyamid in 100 ml 98 gew%iger Schwefelsäure bei 25°C) und wenigstens die wiederkehrenden Struktureinheiten der Formeln I, IV und V aufweisen (-OC-Ar-CO-NH-Ar'-NH-)

    Figure 00080001
    Figure 00080002
    worin -Ar- und -Ar'- die oben definierten Bedeutungen besitzen, und die Anteile der wiederkehrenden Struktureinheiten I, IV und V, bezogen auf die Gesamtmenge dieser Struktureinheiten im Polymeren, innerhalb folgender Bereiche liegen:

  • wiederkehrende Struktureinheit der Formel I: 40 bis 65 Mol %,
  • vorzugsweise 45 bis 55 Mol %,
  • wiederkehrende Struktureinheit der Formel IV: 5 bis 55 Mol %,
  • vorzugsweise 35 bis 45 Mol %, und
  • wiederkehrende Struktureinheit der Formel V: 5 bis 35 Mol %,
  • vorzugsweise 5 bis 25 Mol %.
    • It is also particularly preferred to use aromatic copolyamides in the process according to the invention which have an inherent viscosity of at least 2.4 dl / g, preferably 3.0 to 6.5 dl / g (measured on solutions of 0.5 g polyamide in 100 ml 98 % sulfuric acid at 25 ° C) and at least the recurring structural units of the formulas I, IV and V. (-OC-Ar-CO-NH-Ar'-NH-)
    Figure 00080001
    Figure 00080002
    in which -Ar- and -Ar'- have the meanings defined above, and the proportions of the repeating structural units I, IV and V, based on the total amount of these structural units in the polymer, are within the following ranges:
  • recurring structural unit of the formula I: 40 to 65 mol%,
  • preferably 45 to 55 mol%,
  • recurring structural unit of the formula IV: 5 to 55 mol%,
  • preferably 35 to 45 mol%, and
  • recurring structural unit of the formula V: 5 to 35 mol%,
  • preferably 5 to 25 mol%.

    • Aramide dieses Typs sind aus der EP-A-499,230 bekannt, welche ebenfalls Gegenstand der vorliegenden Beschreibung ist.Aramids of this type are known from EP-A-499,230, which also The subject of the present description is.

    Besonders bevorzugt setzt man Typen dieser Aramide ein, worin -Ar- und -Ar'- 1,4-Phenylen sind.Types of these aramids are particularly preferably used, in which -Ar- and -Ar'- Are 1,4-phenylene.

    Zur Durchführung des erfindungsgemäßen Verfahrens können die Aramid-Multifilamente in Form von Kurzschnitt, Stapelfasern oder von Endlosfilamenten eingelagert werden. Stapelfasern besitzen beispielsweise eine Stapellänge von 1,5 bis 48 mm, vorzugsweise 3 bis 24 mm, insbesondere 4 bis 12 mm. Formkörper enthaltend Endlosfilamente können beispielsweise unidirektional verstärkte Formkörper oder im Wickelverfahren verstärkte Formkörper sein.The aramid multifilaments can be used to carry out the method according to the invention in the form of short cuts, staple fibers or continuous filaments be stored. For example, staple fibers have a staple length of 1.5 to 48 mm, preferably 3 to 24 mm, in particular 4 to 12 mm. Shaped articles containing continuous filaments can, for example, be unidirectional reinforced molded body or reinforced molded body in the winding process.

    Hinsichtlich des Einzelfasertiters ist das erfindungsgemäße Verfahren keinen Beschränkungen unterworfen. Typische Einzelfasertiter liegen oberhalb von 1,0 dtex, vorzugsweise im Bereich von 1,7 bis 15 dtex.With regard to the single fiber titer, the method according to the invention is not Subject to restrictions. Typical single fiber titers are above 1.0 dtex, preferably in the range from 1.7 to 15 dtex.

    Endlosfilamente werden im allgemeinen als Multifilamente eingelagert. Deren Gesamttiter liegt typisch im Bereich von 840 bis 18400 dtex. Es wurde gefunden, daß der Festigkeitsanstieg beim Einsatz von Multifilamenten mit höheren Gesamttitern ausgeprägter ist, weshalb der Einsatz solcher Multifilamente besonders bevorzugt ist.Continuous filaments are generally stored as multifilaments. Their Total titer is typically in the range from 840 to 18400 dtex. It was found that the increase in strength when using multifilaments with higher overall titles is more pronounced, which is why the use of such Multifilaments is particularly preferred.

    Das Einmischen von Stapelfasern in die Matrix kann mit konventionellen Mischaggregaten erfolgen; so kann beispielsweise das Einlagern von Stapelfasern in die Matrix aus hydraulisch abbindenden Materialien mittels praxisüblicher Zwangs-, Pflugschar- und anderer derartiger Mischer erfolgen. Die Matrix liegt vorzugsweise als anorganisches Material vor, wie in der Form von Feinanteilen, wie Gips, Zement, Kalksteinmehl, bis zu Grobbestandteilen, wie Sand, Kies und Steinen. Das Einmischen in das anorganische Material kann in trockenem oder in feuchtem Zustand erfolgen.Mixing staple fibers into the matrix can be done with conventional Mixing units take place; for example, the storage of Staple fibers in the matrix of hydraulically setting materials by means of practical forced, ploughshare and other such mixers take place. The matrix is preferably in the form of an inorganic material, such as in the form from fine particles, such as gypsum, cement, limestone powder, to coarse particles, like sand, gravel and stones. Mixing into the inorganic material can done in a dry or moist state.

    Das Einbringen von Multifilamenten in die Matrix kann ebenfalls nach an sich bekannten Verfahren erfolgen, beispielsweise durch Einlagern vorgeformter Körper aus Multifilamenten mit hydraulisch abbindenden Materialien; diese ergeben nach dem Abbinden den gewünschten Formkörper. Dabei handelt es sich vorzugsweise um unidirektional verstärkte Formkörper oder um im Wickelverfahren verstärkte Formkörper.The introduction of multifilaments into the matrix can also be done in itself Known methods take place, for example by storing preformed Multifilament body with hydraulically setting materials; this result in the desired shaped body after setting. This is what it is about preferably unidirectionally reinforced molded articles or in Shaped body reinforced molding.

    Ferner wurde gefunden, daß der Erhalt oder der Anstieg der Zugfestigkeit bei der Langzeitlagerung im wesentlichen erhalten bleibt. Die Eigenschaftsverbesserung der Multifilamente läßt sich insbesondere bei der Herstellung und Anwendung von Formkörpern ausnutzen, welche aus einer Kombination der erfindungsgemäß zu verwendenden Aramid-Multifilamente und einer wässrigen Abmischung eines hydraulisch abbindenden anorganischen Materials hergestellt werden. Die Erfindung betrifft daher auch die derart erhältlichen Formkörper.It was also found that the retention or increase in tensile strength at long-term storage is essentially preserved. The property improvement The multifilaments can be used in particular in the manufacture and Exploit the use of moldings, which consist of a combination of aramid multifilaments to be used according to the invention and an aqueous one Mixture of a hydraulically setting inorganic material produced will. The invention therefore also relates to the moldings obtainable in this way.

    Die erfindungsgemäß behandelten oder zu behandelnden Multifilamente lassen sich zur Herstellung von Gips, Zement, Mörteln, Putzen, Estrich oder Beton einsetzen.Leave the multifilaments treated or to be treated according to the invention for the production of plaster, cement, mortar, plaster, screed or concrete deploy.

    Die folgenden Beispiele erläutern die Erfindung, ohne diese zu begrenzen.The following examples illustrate the invention without limiting it.

    Allgemeine ArbeitsvorschriftGeneral working instructions

    In den folgenden Beispielen werden Multifilamente eingesetzt, welche aus einem Aramid auf der Basis von 100 Mol % Terephthalsäure, 25 Mol % para-Phenylendiamin, 25 Mol % 1,4-Bis-(4-aminophenoxy)-benzol und 50 Mol % 3,3'-Dimethylbenzidin (Aramid I) bzw. aus einem Aramid auf der Basis von 100 Mol % Terephthalsäure, 50 Mol % para-Phenylendiamin, 15 Mol % 1,4-Bis-(4-aminophenoxy)-benzol und 35 Mol % 3,4'-Diaminodiphenylether (Aramid II) bestehen.In the following examples, multifilaments are used, which consist of a Aramid based on 100 mol% terephthalic acid, 25 mol% para-phenylenediamine, 25 mol% 1,4-bis (4-aminophenoxy) benzene and 50 mol% 3,3'-dimethylbenzidine (aramid I) or from an aramid based on 100 mol% terephthalic acid, 50 mol% para-phenylenediamine, 15 mol% 1,4-bis (4-aminophenoxy) benzene and 35 mole% 3,4'-diaminodiphenyl ether (aramid II) exist.

    Das Faserkabel wird durch ein übliches Naßspinnverfahren durch Verspinnen einer Polymerlösung in N-Methylpyrrolidon in ein Fällbad und eine Nachbehandlung umfassend Waschen, Verstrecken und Trocknen erzeugt.The fiber tow is spun by a conventional wet spinning method a polymer solution in N-methylpyrrolidone in a precipitation bath and a Post-treatment comprising washing, stretching and drying.

    Die Einlagerung erfolgt in Zementfiltrat: Portland Zement PZ 35 (200 g in 1 l Wasser).The storage takes place in cement filtrate: Portland cement PZ 35 (200 g in 1 l Water).

    Beispiele 1-4:Examples 1-4:

    Ein Faserkabel aus Aramid I des Gesamttiters von 1680 dtex wird 24 Stunden lang in Zementfiltrat des pH-Werts von 12,5 und bei unterschiedlichen Temperaturen gelagert. In Tabelle 1 werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 1 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 1 2 3 4 Lagertemperatur (°C) - 22 60 95 Zugfestigkeit (cN/tex) 204 221 226 230 Modul (N/tex) 60,3 60,7 60,2 58,5 Reißdehnung (%) 3,4 3,7 3,8 4,0 An aramid I fiber cable with a total titre of 1680 dtex is stored for 24 hours in cement filtrate with a pH of 12.5 and at different temperatures. Table 1 shows the tensile strengths, moduli and elongations at break of the samples after storage. Example 1 shows the values for the untreated fiber. Example No. 1 2nd 3rd 4th Storage temperature (° C) - 22 60 95 Tensile strength (cN / tex) 204 221 226 230 Module (N / tex) 60.3 60.7 60.2 58.5 Elongation at break (%) 3.4 3.7 3.8 4.0

    Beispiele 5-8:Examples 5-8:

    Ein Faserkabel aus Aramid I des Gesamttiters von 1100 dtex wird 24 Stunden lang in Natronlauge unterschiedlichen pH-Werts bei 60°C gelagert. In Tabelle 2 werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 5 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 5 6 7 8 pH-Wert - 10 12 14 Zugfestigkeit (cN/tex) 196 203 201 207 Modul (N/tex) 60,3 60,2 59,1 58,5 Reißdehnung (%) 3,5 3,6 3,6 3,8 An aramid I fiber cable with a total titer of 1100 dtex is stored for 24 hours in sodium hydroxide solution at different pH values at 60 ° C. Table 2 shows tensile strengths, moduli and elongations at break of the samples after storage. Example 5 shows the values for the untreated fiber. Example No. 5 6 7 8th PH value - 10th 12th 14 Tensile strength (cN / tex) 196 203 201 207 Module (N / tex) 60.3 60.2 59.1 58.5 Elongation at break (%) 3.5 3.6 3.6 3.8

    Beispiele 9-12:Examples 9-12:

    Ein Faserkabel aus Aramid I des Gesamttiters von 1680 dtex wird 24 Stunden lang in Natronlauge unterschiedlichen pH-Werts bei 60°C gelagert. In Tabelle 3 werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 9 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 9 10 11 12 pH-Wert - 10 12 14 Zugfestigkeit (cN/tex) 204 207 229 231 Modul (N/tex) 60,3 60,4 61,2 61,4 Reißdehnung (%) 3,4 3,5 3,9 3,9 An aramid I fiber cable with a total titre of 1680 dtex is stored for 24 hours in sodium hydroxide solution of different pH values at 60 ° C. Table 3 shows tensile strengths, moduli and elongations at break of the samples after storage. Example 9 shows the values for the untreated fiber. Example No. 9 10th 11 12th PH value - 10th 12th 14 Tensile strength (cN / tex) 204 207 229 231 Module (N / tex) 60.3 60.4 61.2 61.4 Elongation at break (%) 3.4 3.5 3.9 3.9

    Beispiele 13-16:Examples 13-16:

    Ein Faserkabel aus Aramid II des Gesamttiters von 1100 dtex wird 24 Stunden lang in Natronlauge unterschiedlichen pH-Werts bei 60°C gelagert. In Tabelle 4 werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 13 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 13 14 15 16 pH-Wert - 10 12 14 Zugfestigkeit (cN/tex) 225 228 230 231 Modul (N/tex) 47,4 46 47 46 Reißdehnung (%) 4,6 4,8 4,8 4,9 An aramid II fiber cable with a total titre of 1100 dtex is stored for 24 hours in sodium hydroxide solution of different pH values at 60 ° C. Table 4 shows tensile strengths, moduli and elongations at break of the samples after storage. Example 13 shows the values for the untreated fiber. Example No. 13 14 15 16 PH value - 10th 12th 14 Tensile strength (cN / tex) 225 228 230 231 Module (N / tex) 47.4 46 47 46 Elongation at break (%) 4.6 4.8 4.8 4.9

    Beispiele 17-20:Examples 17-20:

    Ein Faserkabel aus Aramid I des Gesamttiters von 1100 dtex wird 24 Stunden lang in Zementfiltrat des pH-Werts von 12,5 und bei unterschiedlichen Temperaturen gelagert. In Tabelle 5 werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 17 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 17 18 19 20 Lagertemperatur (°C) - 22 60 95 Zugfestigkeit (cN/tex) 196 206 213 211 Modul (N/tex) 60,3 59,9 59,3 57,0 Reißdehnung (%) 3,5 3,6 3,7 3,9 An aramid I fiber cable with a total titer of 1100 dtex is stored for 24 hours in cement filtrate with a pH of 12.5 and at different temperatures. Table 5 shows tensile strengths, moduli and elongations at break of the samples after storage. Example 17 shows the values for the untreated fiber. Example No. 17th 18th 19th 20th Storage temperature (° C) - 22 60 95 Tensile strength (cN / tex) 196 206 213 211 Module (N / tex) 60.3 59.9 59.3 57.0 Elongation at break (%) 3.5 3.6 3.7 3.9

    Beispiele 21-24:Examples 21-24:

    Ein Faserkabel aus Aramid II des Gesamttiters von 1100 dtex wird 24 Stunden lang in Zementfiltrat des pH-Werts von 12,5 und bei unterschiedlichen Temperaturen gelagert. In Tabelle 6 werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 21 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 21 22 23 24 Lagertemperatur (°C) - 22 60 95 Zugfestigkeit (cN/tex) 225 230 229 225 Modul (N/tex) 47,4 45,6 45,7 45,2 Reißdehnung (%) 4,6 4,9 4,8 4,8 An Aramid II fiber cable with a total titer of 1100 dtex is stored for 24 hours in cement filtrate with a pH of 12.5 and at different temperatures. Table 6 shows tensile strengths, moduli and elongations at break of the samples after storage. Example 21 shows the values for the untreated fiber. Example No. 21 22 23 24th Storage temperature (° C) - 22 60 95 Tensile strength (cN / tex) 225 230 229 225 Module (N / tex) 47.4 45.6 45.7 45.2 Elongation at break (%) 4.6 4.9 4.8 4.8

    Beispiele 25-35:Examples 25-35:

    Ein Faserkabel aus Aramid I des Gesamttiters von 1680 dtex wird über einen längeren Zeitraum in Zementfiltrat des pH-Werts 12,5 bei 80°C gelagert. Von Zeit zu Zeit werden Faserproben entnommen deren mechanische Eigenschaften ermittelt werden. In Tabelle 7 werden Zugfestigkeiten, Moduli und Reißdehnungen der unterschiedlich lange gelagerten Proben angegeben. Beispiel Nr. 25 26 27 28 29 30 31 32 33 34 35 Lagerzeit (Tage) 0 1 2 3 4 5 9 15 20 26 30 Zugfestigkeit 210 214 221 227 230 227 228 227 228 228 232 (cN/tex) Modul (N/tex) 60,3 58,5 59 58,2 58,2 58,0 58,6 59,0 58,0 58,2 59,3 Reißdehnung (%) 3,4 3,8 3,9 4,0 4,0 4,0 4,0 3,9 4,0 4,0 4,0 An aramid I fiber cable with a total titre of 1680 dtex is stored in cement filtrate with a pH value of 12.5 at 80 ° C for a longer period of time. From time to time, fiber samples are taken whose mechanical properties are determined. Table 7 shows tensile strengths, moduli and elongations at break of the samples stored for different lengths. Example No. 25th 26 27 28 29 30th 31 32 33 34 35 Storage time (days) 0 1 2nd 3rd 4th 5 9 15 20th 26 30th tensile strenght 210 214 221 227 230 227 228 227 228 228 232 (cN / tex) Module (N / tex) 60.3 58.5 59 58.2 58.2 58.0 58.6 59.0 58.0 58.2 59.3 Elongation at break (%) 3.4 3.8 3.9 4.0 4.0 4.0 4.0 3.9 4.0 4.0 4.0

    Beispiele 36-46:Examples 36-46:

    Ein Faserkabel aus Aramid I des Gesamttiters von 1100 dtex wird über einen längeren Zeitraum in Zementfiltrat des pH-Werts 12,5 bei 80°C gelagert. Von Zeit zu Zeit werden Faserproben entnommen deren mechanische Eigenschaften ermittelt werden. In Tabelle 8 werden Zugfestigkeiten, Moduli und Reißdehnungen der unterschiedlich lange gelagerten Proben angegeben. Beispiel Nr. 36 37 38 39 40 41 42 43 44 45 46 Lagerzeit (Tage) 0 1 2 3 4 5 9 15 20 26 30 Zugfestigkeit 201 209 211 206 211 212 212 210 209 212 213 (cN/tex) Modul (N/tex) 60 58,0 57,0 58,0 58 58,8 59,3 57,4 57,9 58,1 58,2 Reißdehnung (%) 3,5 3,7 3,9 3,7 3,8 3,8 3,7 3,8 3,8 3,8 3,8 An aramid I fiber cable with a total titer of 1100 dtex is stored in cement filtrate with a pH value of 12.5 at 80 ° C for a longer period of time. From time to time, fiber samples are taken whose mechanical properties are determined. Table 8 shows tensile strengths, moduli and elongations at break of the samples stored for different lengths. Example No. 36 37 38 39 40 41 42 43 44 45 46 Storage time (days) 0 1 2nd 3rd 4th 5 9 15 20th 26 30th tensile strenght 201 209 211 206 211 212 212 210 209 212 213 (cN / tex) Module (N / tex) 60 58.0 57.0 58.0 58 58.8 59.3 57.4 57.9 58.1 58.2 Elongation at break (%) 3.5 3.7 3.9 3.7 3.8 3.8 3.7 3.8 3.8 3.8 3.8

    Beispiele 47-57:Examples 47-57

    Ein Faserkabel aus Aramid II des Gesamttiters von 1100 dtex wird über einen längeren Zeitraum in Zementfiltrat des pH-Werts 12,5 bei 80°C gelagert. Von Zeit zu Zeit werden Faserproben entnommen deren mechanische Eigenschaften ermittelt werden. In Tabelle 9 werden Zugfestigkeiten, Moduli und Reißdehnungen der unterschiedlich lange gelagerten Proben angegeben. Beispiel Nr. 47 48 49 50 51 52 53 54 55 56 57 Lagerzeit (Tage) 0 1 2 3 4 5 9 15 20 26 30 Zugfestigkeit 212 220 215 214 218 215 225 221 217 225 221 (cN/tex) Modul (N/tex) 45,1 45,0 44,0 45,0 44,0 44,1 45,2 45,8 44,7 45,1 44,2 Reißdehnung (%) 4,7 4,5 4,7 4,5 4,7 4,7 4,8 4,6 4,7 4,8 4,7 An aramid II fiber cable with a total titer of 1100 dtex is stored in cement filtrate with a pH of 12.5 at 80 ° C for a longer period of time. From time to time, fiber samples are taken whose mechanical properties are determined. Table 9 shows tensile strengths, moduli and elongations at break of the samples stored for different lengths. Example No. 47 48 49 50 51 52 53 54 55 56 57 Storage time (days) 0 1 2nd 3rd 4th 5 9 15 20th 26 30th tensile strenght 212 220 215 214 218 215 225 221 217 225 221 (cN / tex) Module (N / tex) 45.1 45.0 44.0 45.0 44.0 44.1 45.2 45.8 44.7 45.1 44.2 Elongation at break (%) 4.7 4.5 4.7 4.5 4.7 4.7 4.8 4.6 4.7 4.8 4.7

    Beispiele 58-65:Examples 58-65:

    In den folgenden Beispielen wurden Multifilamente eingesetzt, welche aus einem Aramid auf der Basis von 100 Mol % Terephthalsäure, 50 Mol % para-Phenylendiamin und 50 Mol % 3,4'-Diaminodiphenylether bestehen.In the following examples, multifilaments were used which consist of an aramid based on 100 mol% terephthalic acid, 50 mol% para-phenylenediamine and 50 mol% of 3,4'-diaminodiphenyl ether.

    Bei dem Multifilamenten handelt es sich um ein nach üblichem Verfahren naßgesponenenes und nachbehandeltes Faserkabel. Die Einlagerung erfolgte in Zementfiltrat: Portland Zement PZ 35 (200 g in 1 l Wasser)The multifilament is a customary process wet-spun and post-treated fiber cable. The storage took place in Cement filtrate: Portland cement PZ 35 (200 g in 1 l water)

    Beispiele 58-61:Examples 58-61:

    Ein Faserkabel aus Filamenten des oben gekennzeichneten Aramids des Gesamttiters von 1700 dtex wurde 24 Stunden lang in Zementfiltrat des pH-Werts von 12,5 und bei unterschiedlichen Temperaturen gelagert. In der folgenden Tabelle werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 58 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 58 59 60 61 Lagertemperatur (°C) - 22 60 95 Zugfestigkeit (cN/tex) 225 225 235 240 Modul (N/tex) 60 60 60 60 Reißdehnung (%) 4 4 4 4 A fiber tow of filaments of the above-identified aramid with a total titer of 1700 dtex was stored for 24 hours in cement filtrate with a pH of 12.5 and at different temperatures. The following table shows tensile strengths, moduli and elongations at break of the samples after storage. Example 58 shows the values for the untreated fiber. Example No. 58 59 60 61 Storage temperature (° C) - 22 60 95 Tensile strength (cN / tex) 225 225 235 240 Module (N / tex) 60 60 60 60 Elongation at break (%) 4th 4th 4th 4th

    Beispiele 62-65:Examples 62-65:

    Ein Faserkabel aus Filamenten des oben gekennzeichneten Aramids des Gesamttiters von 1700 dtex wurde 24 Stunden lang in Natronlauge unterschiedlichen pH-Werts bei 60°C gelagert. In der folgenden Tabelle werden Zugfestigkeiten, Moduli und Reißdehnungen der Proben nach dem Lagern angegeben. Beispiel 62 zeigt die Werte für die unbehandelte Faser. Beispiel Nr. 62 63 64 65 pH-Wert - 10 12 14 Zugfestigkeit (cN/tex) 225 230 245 245 Modul (N/tex) 60 60 60 60 Reißdehnung (%) 4 4 4 4 A fiber cable made of filaments of the above-identified aramid with a total titre of 1700 dtex was stored for 24 hours in sodium hydroxide solution at different pH values at 60 ° C. The following table shows tensile strengths, moduli and elongations at break of the samples after storage. Example 62 shows the values for the untreated fiber. Example No. 62 63 64 65 PH value - 10th 12th 14 Tensile strength (cN / tex) 225 230 245 245 Module (N / tex) 60 60 60 60 Elongation at break (%) 4th 4th 4th 4th

    Claims (14)

    1. A process for maintaining or increasing the tensile strength of multifilaments of aromatic copolyamides which are built up chiefly from para-monomers and are soluble in organic aprotic and polar solvents, in the course of storage in alkaline media, comprising the measures:
      a) production of multifilaments from said aromatic copolyamides by dry or wet spinning processes which are customary per se,
      b) after-treatment of the resulting multifilaments in a manner which is known per se, and
      c) storage of the multifilaments having an overall linear density of 840 to 18,400 dtex in an aqueous slurry or mixture of a hydraulically setting inorganic material, in particular concrete or cement, which has a pH of at least 10 for at least a period of time and at a temperature of 20 to 100°C such that the tensile strength of said fibers, based on the tensile strength of the fibers employed in step c), is at least retained or increased, a subsequent saturated steam treatment in an autoclave not being carried out.
    2. The process as claimed in claim 1, wherein the storage of the multifilaments in step c) is carried out at least for a period of time such that the tensile strength of said multifilaments, based on the tensile strength of the multifilaments employed in step c), is increased by at least 1%, in particular by 2 to 10%.
    3. The process as claimed in claim 1, wherein multifilaments which have an initial tensile strength of at least 120 cN/tex and an initial elasticity modulus, based on 100% elongation, of more than 30 N/tex, are employed in step c).
    4. The process as claimed in claim 1, wherein the aqueous slurry or mixture of a hydraulically setting inorganic material, in particular concrete or cement, has a pH equal to or greater than 12, preferably 12 to 14.
    5. The process as claimed in claim 4, wherein an aqueous mixture of a hydraulically setting inorganic material is used as the storage medium and storage is carried out after mixing in of the multifilaments and after shaping of the resulting mixture.
    6. The process as claimed in claim 1, wherein the storage is carried out at a temperature of 20 to 60°C.
    7. The process as claimed in claim 1, wherein a multifilament consisting of aromatic copolyamide is employed which has an intrinsic viscosity of at least 2.4 dl/g (measured on solutions of 0.5 g of polyamide in 100 ml of 98% strength by weight sulfuric acid at 25°C) and contains at least the recurring structural units of the formulae I, II and III (-OC-Ar-CO-NH-Ar'-NH-)
      Figure 00230001
      Figure 00240001
      in which -Ar- and -Ar'- are divalent organic radicals in which the valency bonds are in the para-position or a comparable coaxial or parallel position relative to one another,
      R is a C1-C4-alkyl radical, in particular methyl, a C1-C4-alkoxy radical, in particular methoxy, or a chlorine atom,
      R' is an unsubstituted or alkyl-substituted methylene radical or a grouping
      -O-Ar-O-, in which -Ar- assumes the meaning defined above, and the proportions of the recurring structural units I, II and III, based on the total amount of these structural units in the polymer, lie within a range defined by the following corner points:
      point Q corresponding to 5 mol% of structural units of the formula I, 45 mol% of structural units of the formula II and 50 mol% of structural units of the formula III,
      point R corresponding to 45 mol% of structural units of the formula I, 5 mol% of structural units of the formula II and 50 mol% of structural units of the formula III,
      point S corresponding to 60 mol% of structural units of the formula I, 35 mol% of structural units of the formula II and 5 mol% of structural units of the formula III,
      point T corresponding to 20 mol% of structural units of the formula I, 75 mol% of structural units of the formula II and 5 mol% of structural units of the formula III, and
      point U corresponding to 5 mol% of structural units of the formula I, 80 mol% of structural units of the formula II and 15 mol% of structural units of the formula III.
    8. The process as claimed in claim 7, wherein -Ar- and -Ar'- are 1,4-phenylene, R is methoxy or chlorine or, in particular, methyl and R' is -O-1,4-phenylene-O-, the proportions of the amounts of the recurring structural units, based on the total amount of these structural units within the polymer, lying within the following ranges:
      recurring structural unit of the formula I: 15 to 45 mol%,
      recurring structural unit of the formula II: 20 to 70 mol%, and
      recurring structural unit of the formula III: 15 to 50 mol%.
    9. The process as claimed in claim 1, wherein a multifilament consisting of aromatic copolyamide is employed which has an intrinsic viscosity of 2.4 to 6.5 dl/g (measured on solutions of 0.5 g of polyamide in 100 ml of 98% strength by weight sulfuric acid at 25°C) and contains at least the recurring structural units of the formulae I, IV and V (-OC-Ar-CO-NH-Ar'-NH-)
      Figure 00250001
      Figure 00250002
      in which -Ar- and -Ar'- have the meanings defined in claim 7, and the proportions of the recurring structural units I, IV and V, based on the total amount of these structural units in the polymer, lie within the following ranges:
      recurring structural unit of the formula I: 40 to 65 mol%,
      recurring structural unit of the formula IV: 5 to 55 mol%, and
      recurring structural unit of the formula V: 5 to 35 mol%.
    10. The process as claimed in claim 9, wherein -Ar- and -Ar'- are 1,4-phenylene, and wherein the proportions of the amounts of the recurring structural units, based on the total amount of these structural units within the polymer, lie within the following ranges:
      recurring structural unit of the formula I: 45 to 55 mol%,
      recurring structural unit of the formula IV: 35 to 45 mol%, and
      recurring structural unit of the formula V: 5 to 25 mol%.
    11. The process as claimed in claim 1, wherein a multifilament consisting of aromatic copolyamide is employed which has an intrinsic viscosity of at least 2.4 dl/g (measured on solutions of 0.5 g of polyamide in 100 ml of 98% strength by weight sulfuric acid at 25°C) and contains at least the recurring structural units of the formulae I and VI (OC-Ar-CO-NH-Ar'-NH-) and
      Figure 00260001
      in which Ar and Ar' have the meanings defined in claim 7 and the proportions of the recurring structural units I and VI, based on the total amount of these structural units in the polymer, lie within the following ranges:
         formula I: 50 to 60 mol%; formula VI: 40 to 50 mol%.
    12. A shaped article obtainable by the process as claimed in claim 5.
    13. The shaped article as claimed in claim 12, which contains multifilaments having an overall linear density of 840 to 18,400 dtex.
    14. The use of the multifilaments treated or to be treated by the process as claimed in claim 1 for the production of gypsum, cement, mortars, plasters, screed or concrete.
    EP19940100194 1993-01-13 1994-01-07 Process to maintain or to improve the mechanical properties of aromatic copolyamide fibers in alkaline medium and articles containing these fibers Expired - Lifetime EP0606859B1 (en)

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    DE4300626 1993-01-13

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    Families Citing this family (20)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE4401233A1 (en) * 1994-01-18 1995-07-20 Hoechst Ag Bundles of staple fibers made from aromatic polyamides with improved dispersibility in viscous matrices, and process for producing fiber-reinforced composites
    US6001476A (en) * 1997-04-18 1999-12-14 Selivansky; Dror Method of upgrading existing nylon fibers and use of same for reinforcement of cementitious composites
    DE10159339B4 (en) * 2000-12-05 2004-04-08 Akzo Nobel N.V. Filler and use of such a filler
    DE10159337B4 (en) * 2000-12-05 2004-04-08 Akzo Nobel N.V. Filler and use of such a filler
    US7669236B2 (en) * 2004-11-18 2010-02-23 Biogy, Inc. Determining whether to grant access to a passcode protected system
    US20060107312A1 (en) * 2004-11-18 2006-05-18 Michael Fiske System for handing requests for access to a passcode protected entity
    US7886155B2 (en) 2004-12-20 2011-02-08 Biogy, Inc. System for generating requests to a passcode protected entity
    US7979716B2 (en) 2004-11-18 2011-07-12 Biogy, Inc. Method of generating access keys
    US20060107315A1 (en) * 2004-11-18 2006-05-18 Michael Fiske System that uses access keys
    US20090228714A1 (en) * 2004-11-18 2009-09-10 Biogy, Inc. Secure mobile device with online vault
    US8209751B2 (en) * 2004-11-18 2012-06-26 Biogy, Inc. Receiving an access key
    US7707622B2 (en) 2004-11-18 2010-04-27 Biogy, Inc. API for a system having a passcode authenticator
    US7565548B2 (en) * 2004-11-18 2009-07-21 Biogy, Inc. Biometric print quality assurance
    US7770018B2 (en) * 2004-11-18 2010-08-03 Biogy, Inc. Setting up a security access system
    US20060107309A1 (en) * 2004-11-18 2006-05-18 Michael Fiske Using an access key
    US7702911B2 (en) * 2004-11-18 2010-04-20 Biogy, Inc. Interfacing with a system that includes a passcode authenticator
    US20080288786A1 (en) * 2004-12-20 2008-11-20 Michael Stephen Fiske System with access keys
    JP5886320B2 (en) * 2011-01-04 2016-03-16 テイジン・アラミド・ビー．ブイ． Electrical insulation paper
    KR101386429B1 (en) * 2012-12-28 2014-04-29 코오롱인더스트리 주식회사 Method of dry-spinning para-aramid fiber
    EP3286363B1 (en) * 2015-04-22 2019-01-30 Teijin Aramid B.V. Cord comprising multifilament para-aramid yarn comprising non-round filaments

    Family Cites Families (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    NL53915C (en) * 1938-10-03
    US2781242A (en) * 1954-02-05 1957-02-12 Du Pont Process of improving the hand of polyethylene terephthalate fabric by heat shrinking and hydrolyzing the fabric
    NL212981A (en) * 1956-12-14
    JPS53138422A (en) * 1977-05-11 1978-12-02 Asahi Chemical Ind Formed product of fiberrreinforced cement
    JPS58151363A (en) * 1982-03-01 1983-09-08 帝人株式会社 Fiber reinforced cement product
    JPS61183155A (en) * 1985-02-09 1986-08-15 鹿島建設株式会社 Manufacture of fiber reinforced cement concrete products
    DE3674620D1 (en) * 1985-03-23 1990-11-08 Hoechst Ag MOLDED COMPOSITIONS FROM AROMATIC COPOLYAMIDES AND METHOD FOR THEIR PRODUCTION.
    DE3582499D1 (en) * 1985-11-28 1991-05-16 Mitsui Constr FIBER REINFORCED MOLDED CEMENT BODY.
    US4693749A (en) * 1985-12-20 1987-09-15 E. I. Dupont De Nemours And Company Cement reinforcement
    US5306782A (en) * 1989-05-08 1994-04-26 American Cyanamid Company Surface-modified polyacrylonitrile fibrous substrates
    US4974522A (en) * 1989-06-09 1990-12-04 Relmech Manufacturing Limited Cold-molded cementitious composites reinforced with surface-modified polyamide fibres and method of preparing same
    DE3929376C1 (en) * 1989-09-05 1991-04-18 E.I. Du Pont De Nemours And Co., Wilmington, Del., Us
    DE4010941A1 (en) * 1990-04-05 1991-10-10 Hoechst Ag METHOD FOR PRODUCING AROMATIC POPYAMIDES WITH HIGH HYDROLYSIS RESISTANCE
    US5290907A (en) * 1991-02-14 1994-03-01 Hoechst Aktiengesellschaft Automatic copolyamide
    US5266672A (en) * 1991-07-02 1993-11-30 Hoechst Aktiengesellschaft Aromatic copolyaide from diamino benzanilide
    DE4139747A1 (en) * 1991-12-03 1993-06-09 Bayer Ag, 5090 Leverkusen, De FUEL-BASED, OPTICALLY ACTIVE PEARL POLYMERISES
    CZ134893A3 (en) * 1992-07-08 1994-02-16 Hoechst Ag Aromatic copolyamides, process of their preparation and objects made therefrom

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